Alkyl dimethyl benzyl ammonium naphthenate



- Patented Aug. 22, 1950 ALKYL DIMETHYL BENZYL AM'MONIUM NAPHTHENATEMilton Nowak, Brooklyn, N. Y., assignor to Naodex Products Co., Inc.,Elisabeth, N. 1., a corporation of New York No Drawing. ApplicationNovember 7, 1946, Serial No. 108,445

2 Claims.

This invention is an agent useful for pest control and for immunizingarticles of commerce against the ravages of destructive macro andmicro-organisms, such as bacteria, fungi, insects, various forms ofmarine life, etc.

Heretofore certain agents, variously known as toxicants, pest controlagents, or fungicides have been widely employed. Such agents have,however, lacked certain important characteristics which limited eitheror both their utility and scope of application. For example, cellulosicfabrics, particularly cotton fabrics, when exposed to the weather,commonly suffer from the attacks of cellulose destroying fungi. Whenattempts were made in the past to protect such fabrics by known pestcontrol agents, certain dimculties were encountered. Fungicides havecommonly been used in this connection, but they have been of suchrelatively low activity that relatively high percentages of them wereneeded to protect the fabric, and, in many instances, such protectionresulted in undesirable coloring of such fabric. Still others lackedchemical stability and decomposed as the fabric aged, particularly whenexposed to the weather. Not uncommonly this decomposition has beenaccompanied by an ancillary reaction causing chemical degradation of thefabric which it was desired to protect. The protection of fabricsdestined for outdoor use against fungus attack without impartingundesirable characteristics to the fabric has constituted a real problemin the past. I

These and other weaknesses of knownfungus and pest control agents haveprompted me to carry out extended research work and experimentation inan eilort to develop a better protective agent which would be devoid ofthe disadvantages to which I have referred and others.

As a result of this protracted research and investigation, a certaingroup of chemical compounds has been produced which are found to beideally suited as pest control agents adapted for a wide variety ofuses, particularly as immuniz'ing or pest control agents against fungiand bacteria. These compounds are oil-soluble quaternary ammoniumcompounds and more particularly quaternary ammonium salts. By quaternaryammonium salts is meant those substituted ammonium salts wherein thefour valences (c1. zoo-404) of nitrogen are linked to organic radicals,while the fifth valence is linked to an anion.

These compounds are characterized by the following structural formula:

l 5 R1 Rt where three groups are replaced by the trivalent ringstructure and X is naphthenic acid, which is a substantiallywater-insoluble and oil-soluble organic acid.

Among examples of the quaternary ammonium compounds of this inventionare:

Dodecyldimethylbenzyl ammonium naphthenate Lauryl pyridinium naphthenateAlkyl dimethyl benzyl ammonium naphthenate 46 Alkyl dimethyl benzylammonium oleate Lauryl pyridinium oleate 9-octadecenyl dimethyl ethylammonium naphthenate 9-octadecenyl dimethyi ethyl ammonium oleate 50Cetyl dimethyl benzyl ammonium'naphthenate asiaoas cetyl dimethyl bensylammonium 2-ethyl hexo- Cetyl diniethyl benzyl ammonium tallate Cetyldimethyl benzyl ammonium alkyi sulionate fl octadecenyl dimethyl ethylammonium 2-ethylhexoate v O-octadecenyl dimethyl ethyl ammonium tallateiI-octadecenyl dimethyl ethyl ammonium alkyl suli'onate Alkyl dimethylbenzyl ammonium 2-ethylhexoate Alhyl dimethyl benzyl ammonium tallateAlkyl dimethyl benzyl ammonium alkyl sulfonate Lauryl pyridiniumz-ethylhexoate Lauryl pyridinium tallate Lauryl pyridinium alkylsulfonate Tetraethyl ammonium naphthenate Dimethvl ethyl propyl ammoniumnaphthenate Lauryl pyridinium naphthenate z-ethylhexoate combinationLauryl pyridinium naphthenate dodecyl dimethyl benzyl ammoniumnaphthenate combination Alkyl dimethyl benzyl ammonium laurate Alkyldimethyl benzyl ammonium linoleate Didodecyldimethyl ammoniumnaphthenate Dodecyldimethylbenzyl ammonium mono-octyl phthalateDodecyldimethyl-o-chlorbenzyl ammonium linoleate Diisobutylphenoxyethoxyethyldimethyl benzyl ammonium 2-ethylhexoate Laurylpyridinium-p-tert.-amylphenoxyacetate p-Tert.-octylphenoxyethoxyethyldimethylbenzyl ammonium oleate N-(lauric acidester of colamino-formyl methyl) dimethyl benzyl ammonium naphthenateDodecyldimethylbenzyl ammonium laurate.

Exhaustive researches in the production of the quaternary ammonium saltsof this invention have been carried out in connection with a greatnumber of acids (represented by X in the structural formula) and it hasbeen found that all the many water-insoluble and oil-soluble acidstested were operative in the carrying out of this invention. In fact nooil-soluble and waterinsoluble organic acid has been found which isinoperative and the tests therefore proved that all oil-soluble andwater-insoluble organic acids will function satisfactorily in theproduction of the novel chemical compound of this invention and allcompounds thus produced are oil-soluble and substantiallywater-insoluble.

These compounds may be prepared by a number of different methods. Theymay be obtained as the pure compounds, but it is also practical toprepare these in the form of solutions in various organic solvents,including benzine. They may also be prepared in other vehicles in whichthey may be soluble, such as synthetic resin solutions, etc.

The following examples are illustrative of the present invention.

Example 1.-Preparation of dodecyl dimethyl benzyl ammonium naphthenate170 grams (.25 M) of 50% dodecyl dimethyl benzyl amonium chloride aredissolved in 500 grams ethyl alcohol and heated with agitation to 60' C.A soap is then prepared consisting of grams of a 50% solution of sodiumhydroxide dissolved in 300 grams of ethyl alcohol to which has ben added55.9 grams (.25 M) of naphthenic acid (acid number 251). The soap shouldtest acid to phenol-phthalein. This soap is added slowly, underagitation, to the previously pre- 4paredaolutionofdodecyldimetbylbensyiammonlum chloride and the resultingsolution is ltrippedofalcoholandwaterinvacuoata bath temperatureof 100C. 'Iheresulting productis'abrownviscous'liquidwhichshouldbemteredthmughasteamfimneltoremdvetheprecipitatedlodiumchlorideofwhichiigrams (.25ll)isrecovered.Theresultingdodecyldimethyl benzyl ammonium naphthenate is soluble inbenaol, toluol, mineral spirits, mineral oil,

linseed oil and all the common fat solvents.

trample l-Preparation of mixed alley! dimethyl benzylammoniamnaphthenate solution) 786 grams (1 ll) of 50% mixed alkyi dimethylbenzyl amonium chloride (derived from amines obtained from cocoanutfatty acids and indicating a mixture of alkyl chains such asoccur incocoanut oil and averaging 12 carbon atoms in length), are added to apreviously prepared soap solutionconsistingofiograms (1M) ofaodiumhydroxide, 200 grams of water and 247 grams of naphthenic acid (acidnumber 228). This soap should test acid to phenolphthalein. Theresulting solution is stripped of water and alcohol in vacuo" at a bathtemperature of 100' C. when dry, 242 grams of Celloeolve" (ethyleneglycol monoethyl ether) or alcohol (ethyl) are added and the resultingsolution filtered. 58 grams of sodium chloride are recovered and the endproduct is a free flowing light amber liquid, soluble in xylol, mineraloil, linseed oil and the common fat solvents.

Example 3.-Preparation of i-octadeeenrl dimethyl ethyl ammoniumnaphthenate 134 grams (.25 M) of D-octadecenyl dimethyl ethyl ammoniumbromide are dissolved in 500 grams of ethyl alcohol and heated withagitation to 60 C. A soap is then prepared consisting of 28 grams of a50% aqueous solution of potassium hydroxide dissolved in 300 grams ofethyl alcohol, to which has been added 55.9 grams (.25 M) of naphthenicacid (acid number 251). The soap should test acid to phenolphthalein.This soap is added slowly, under agitation, to the previously preparedsolution of Q-octadecenyl dimethyl ethyl ammonium bromide and theresulting mixture is stripped of alcohol and water under water vacuum ata bath temperature of C. The resulting product is an amber viscousliquid requiring filtration through a steam funnel to remove theprecipitated potassium bromide of which 29.7 grams is recovered. The9-octadecenyl dimethyl ethyl ammonium naphthenate issoluble in benzol,toluol, mineral spirits, mineral oil, linseed oil and all the common fatsolvents.

Example 4.Preparation of cetyl dimethyl benzyl ammonium naphthenate381.5 grams (.25 M) of 25% cetyl dimethyl benzyl ammonium chloride aredissolved in 500 grams of ethyl alcohol and heated with agitation to 60C. A soap is then prepared consisting of 20 grams of a 50% aqueoussolution of sodium hydroxide dissolved in 300 grams of ethyl alcohol towhich is added 55.9 grams (.25 M) of naphthenic acid (acid number 251).The soap should test acid to phenolphthalein. This soap is added slowlyunder agitation to the previously prepared solution of cetyl dimethylbenzyl ammonium chloride and the resulting mixture is stripped ofalcohol and water under vacuum at a bath temperature of 100 C. Theproduct is an amber viscous liquid requiring filtration through a steamfunnel to remove the preciptated sodium chloride, of which 14 grams (.25M) are recovered. The product is soluble in benzol, toluol, mineralspirits, mineral oil, linseed oil and all the common fat solvents.

In a similar manner a plurality of quaternary raw materials may bereacted with a plurality of acids within the purview of this invention.

The end products of the foregoing examples may be used in practice insolution or otherwise as the fungicidal agent. However, these fungicidalagents may be used in combinations, such, for example, as combinationsof such quaternary compounds plus other fungicidal agents, such asmetallic naphthenates, oleates, tallates, or the like.

In the majority of examples hereinbefore given it has been shown how theend products may be made by reacting water-soluble quaternary ammoniumsalts with a sodium or potassium salt of a water-insoluble organic acidto obtain the end products. The preparation of the watersolubiequaternary ammonium compound itself may be carried out in accordancewith a number of well known conventional methods.

In other examples given, the end product has been made by reactingtogether the water-insoluble organic acid with the water-solublehydroxide of the quaternary ammonium compound. Such hydroxide quaternaryammonium compounds may likewise be prepared by conventional methods. Itis to be understood further that the preparation of the end products ofthis invention are not necessarily limited to the process steps given inthe examples which have been advanced for the purpose of illustration.

The compounds prepared in accordance with this invention have been shownby tests to be highly effective as pest control agents. For example, thecompound made according to Example 1 was applied on a typical awningfabric oz. duck). It was applied in various concentrations ranging fromas little as 25% to 20% per weight of fabric. These various treatedfabric specimens together with an untreated fabric specimen control wereexposed to many different conditions among them weathering, burial incomposted soil rich in micro-organisms, exposed in a high humidity roomfavoring mildew growth, etc. It was found that even the presence of aslittle as .25% of this composition already had a discernible effect uponthe resistance of the fabric to rotting and mildew which are caused byfungi. At the levels of 1% and higher, the treated fabric remainedunaffected by the fungi activities even when exposed to them for as longas six months.

The untreated fabric by comparison lost its tensile strength entirelyupon two weeks exposure to the soil and it lost substantially all of itsstrength when exposed to high humidity for two months. There was nosecondary chemical effect of this compound upon the fabric; that is, thetreated fabric did not suffer chemically from the compound even whenexposed to the weather for as long as six months.

In another series of tests, a number of the compounds enumerated in thevarious examples above were investigated as pest control agents inconnection with economic crops. For this purpose they were applied inthe form of their aqueous emulsions and they were also applied afterfirst being diluted with inert carriers, such as bentonite clays. Thepreliminary results show great promise for their performance as pestcontrol agents in the field of economic crops. In still another test,the compounds described in the various examples were checked for theirefiectiveness in coping with certain bacterial attacks upon manyarticles of commerce; for example, they were used to protect caseinpaints from decomposition and they performed very satisfactorily forsuch purposes.

The agents of this composition may also be used as additives to manyother film-forming compositions and penetrants in addition to theiruseful role in casein paints. For example, they may be introduced intovarnishes, water repellants for textiles and wood, plastics, linoleum,oil paints, polishes, waxes, and a wide variety of other products. Theyare useful as pest control agents in these compositions and they alsohave a pronounced protective effect upon the articles of commerce towhich these compositions are applied. For example, the use of a waterrepellant upon a tent fabric may reduce the water permeability of thfabric, but would not protect the fabric from rotting due to fungusgrowth. The inclusion of the agent of this invention in a waterrepellant composition would protect the fabric treated from such fungusgrowth.

The foregoing detailed description sets forth the invention in itspreferred practical form. but the invention is to be understood as fullycommensurate with the appended claims.

Having thus fully described the invention, what I claim as new aiddesire to secure by Letters Patent is:

1. A substantially water-insoluble and substantially benzlne-solublealkyl dimethyl benzyl ammonium naphthenate wherein the alkyl groupcontains from 12 to 18 carbon atoms.

2. A substantially water-insoluble and substantially benzine-solubledodecyl dimethyl benzyl ammonium naphthenate.

MILTON NOWAK.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,079,613 .Holt May 11, 19372,115,250 Bruson Apr, 26, 1938 2,137,465 Thackston Nov. 22, 19382,176,896 Epstein Oct. 24, 1939 2,295,504 Shelton Sept. 8, 19422,295,505 Shelton Sept. 8, 1942 2,302,805 Schussler Nov. 24, 1942 OTHERREFERENCES Alkaline Earth and Heavy Metal Soaps by Elliott, pages144-147 and 171.

1. A SUBSTANTIALLY WATER-INSOLUBLE AND SUBSTANTIALLY BENZINE-SOLUBLEALKYL DIMETHYL BENZYL AMMONIUM NAPHTHENATE WHEREIN THE ALKYL GROUPCONTAINS FROM 12 TO 18 CARBON ATOMS.